Polymer image formation

ABSTRACT

A METHOD OF FORMING AN IMAGE WHICH COMPRISES REACTING A SILVER HALIDE PHOTOGRAPHIC EMULSION HAVING A LATENT IMAGE WITH AT LEAST ONE ACTIVE METHYLENE COMPOUND REPRESENTED BY THE FOLLOWING GENERAL FORMULAS (A), (B) OR (C), TAUTOMERIC ISOMERS THEREOF AND METAL COMPLEX SALTS THEREOF, IN THE PRESENCE OF AT LEAST ONE ADDITIONPOLYMERIZABLE VINYLIDENE MONOMERS OR VINYL MONOMERS, TO POLYMERIZE SAID MONOMER SELECTIVELY AT LATENT IMAGE AREAS   R1-CO-CH(-R3)-CO-R2   IN WHICH R1 AND R2 ARE ALKYL, SUBSTITUTED ALKYL OR PHENYL GROUPS, R3 IS A HYDROGEN ATOM, ALKYL OR SUBSTITUTED ALKYL GROUP, AND R1 MAY FORM A RING WITH R2 OR R3,   R1-C(=X)-CH(-R3)-CO-Y-R2, OR R1-C(-X-R7)=CH-CO-Y-R2   IN WHICH R1 IS HYDROGEN ATOM OR ALKYL GROUP, R2 IS AN ALKYL GROUP, SUBSTITUTED AROMATIC RING OR SODIUM, R3 IS HYDROGEN ATOM, ALKYL SUBSTITUTED ALKYL, CYANO GROUP OR CHLORINE ATOM, R2 AND R3 MAY FORM A RING, R7 IS AN AROMATIC RING WHEN X IS -NH- AND AN ACYL OR ALKYL GROUP WHEN X IS -O-, X IS O, NH OR   C6H5-NH-N&lt;   AND Y IS O OR NH, AND   R2-CH(-R1)-CN   IN WHICH R1 IS HYDROGEN ATOM, ACYL OR PHENYL GROUP AND R2 IS AN ETHOXYCARBONYL OR CYANO GROUP.

Patented Sept. 4, 1973 3,756,820 POLYMER IMAGE FORMATION YoshihideI-layakawa and Masato Satomura, Asaka,

Japan, assignors to Fuji Photo Film (30., LttL, Kauagawa, Japan NoDrawing. Continuation of abandoned application Ser. No. 873,125, Oct.31, 1969. This application Feb. 14, 1972, Ser. No. 226,208

Claims priority, application Japan, Oct. 13, 1968, 43/79,516 Int. Cl.G03c 1/6'8, 5/26 US. Cl. 96-48 R 37 Claims ABSTRACT OF THE DISCLOSURE inwhich R and R are alkyl, substituted alkyl or phenyl groups, R is ahydrogen atom, alkyl or substituted alkyl group, and R may form a ringwith R or R General Formula (b) in which R is hydrogen atom or alkylgroup, R is an alkyl group, substituted aromatic ring or sodium, R ishydrogen atom, alkyl substituted alkyl, cyano group or chlorine atom, 'Rand R may form a ring, R; is an aromatic ring when X is -NH- and an acylor alkyl group when X is O, X is O, NH or and Y is O or NH, and

General Formula o) in which R is hydrogen atom, acyl or phenyl group andR is an ethoxycarbonyl or cyano group.

This is a continuation of application Ser. No. 873,125, filed Oct. 31,1969, and now abandoned.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to a method of forming a polymer image, and more particularly,to a method wherein a high molecular weight compound is selectivelyformed on an area corresponding to a photographic latent image by thereaction of a silver halide photographic emulsion and a reducing agentin the presence of an addition polymerizable compound.

Description of the prior art Various attempts have been proposed topolymerize a vinyl compound by the action of light to thereby form ahigh molecular weight compound, thereby forming an image. It has alsobeen proposed to directly cause photopolymerization by the use of asilver halide as a catalyst (cf. British 866,631, S. LeVinos et al.;Photographic Science and Engineering, vol. 6, pp. 222226 (1962)). Inthis reaction, the photo-decomposition product of a silver halide can bea catalyst for the direct polymerization and, consequently, thesensitivity obtained herein is not as high as in the case wherein silverhalide particles are reduced by ordinary development.

It has further been proposed to form, imagewise, highly polymerizedcompounds by polymerizing vinyl compounds using, as a catalyst, a silverimage or unreacted silver halide after the development of an exposedsilver halide emulsion with an ordinary developing solution (see BelgianPat. 642,477). This reaction has a disadvantage in that the operationsof developing and polymerizing must be carried out separately. Moreover,it is theoretically of great interest to develop an exposed silverhalide with a reducing compound in the presence of a vinyl compound andto effect polymerization of the vinyl compound by an oxidized product oran intermediate product formed during the redox step, since bothamplifying actions by developing and by chain polymerization can beeffected. It has already been proposed to carry out this reaction usingas the reducing agent a benzenoid compound, such as one having two ormore hydroxyl groups, amino groups or alkylor aryl-substituted aminogroups in the ortho-para-position on a benzene ring to each other (U .8.Pat. 3,019,194, G. Oster; Nature, vol. 180, p. 1275 (1957)).

SUMMARY OF THE INVENTION It is therefore the object of this invention toconvert an image from electromagnetic waves or particle rays into animage of a high molecular weight compound by a simple procedure.

It is another object of this invention to obtain a polymer image havingdesirable properties by applying this method to recording or printing.

A method of forming an image which comprises reacting a silver halidephotographic emulsion having a latent image with at least one activemethylene eompound represented by the following General Formula 2, (b)or (c), tautomeric isomers thereof and metal complex salts thereof, inthe presence of at least one additionpolymerizable vinylidene monomersor vinyl monomers, to polymerize said monomer selectively at latentimage areas General Formula (a) R1 (EH R, l l) in which R and R arealkyl, substituted alkyl or phenyl groups, R, is a hydrogen atom, alkylor substituted alkyl group, and R may form a ring with R or R GeneralFormula (b) s H /Y R2 C or O 0 ll ll 9: l

in which R, is hydrogen atom or alkyl group, R is an alkyl group,substituted aromatic ring or sodium, R is hydrogen atom, alkylsubstituted alkyl, cyano group or chlorine atom, R and R may form aring, R, is an aromatic ring when X is NH- and an acyl or alkyl groupwhen X is O--, X is O, NH or and Y is or NH, and

General Formula (c) N C\ /R:

in which R is hydrogen atom, acyl or phenyl group and R is anethoxycarbonyl or cyano group.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS We, the inventors,have found that when a silver halide is reduced with an active methylenecompound in the presence of a vinyl compound as mentioned hereinafter,the polymerization of said vinyl compound can be initiated. When using asilver halide photographic emulsion as the silver halide, the reactionoccurs more rapidly at a place where silver halide fine crystals possessa developing center, so that the polymerization can occur selectivelyonly at an area where silver halide particles possessing a developingcenter are present. This can be done by the proper selection of reactionconditions and reaction time.

The present invention can be accomplished by Utilizing theabove-mentioned fact that is; that by reacting a silver halide emulsionlayer having a photographic latent image with at least one activemethylene compound in the presence of a polymerizable vinyl compound,one can cause polymerization of said vinyl compound selectively at areaswhere the latent image is present.

The photographic latent image is basically an imagewise change formed ina silver halide photographic emulsion by the action of electromagneticwaves or particle rays. It is ordinarily invisible, but can be convertedinto a visible image by development.

In the photographic emulsion layer utilized for forming a negativeimage, the latent image is formed due to the formation of developmentcenters in silver halide grains irradiated by electromagnetic waves orparticle rays. In a photographic emulsion layer utilized for forming adirect positive image, the latent image is formed by providingdevelopment centers in all of the silver halide grains present in thelayer, and then removing the development centers by irradiation withelectromagnetic waves or particle rays (James and Huggins, Fundamentalsof Photographic Theory 2d ed., published by Morgam & Morgan 1969,chapters 3 and 4).

In the process of the present invention, the aforesaid photographicsilver halide emulsion utilized for forming negative images as well asthe photographic silver halide emulsion utilized for forming positiveimages can be employed.

In the present invention, as a silver halide photographic emulsion thatgives a negative image, an emulsion which is suitable for ordinarydeveloping out processes may be used. Thus, silver chloride, silverbromide, silver chlorobromide, silver iodobromide, and silverchloro-iodobromide photographic emulsions can be used. Chemicalsensitization and optical sensitization which are applicable to ordinaryphotographic emulsions can be applied to the silver halide emulsions foruse in the present invention. Thus, sulfur sensitization and noble metalsensitization are applicable means of chemical sensitization (see, forexample, P. Glafkides, Chimie Photographique, 2d ed., photocinema PaulMonte], Paris 1957, pp. 247-301). As for optical sensitization, opticalsensitizers used for ordinary photographic emulsions such as cyaninedyes and mercocyanine dyes can be used, see, for example, Kikuchi etal., Kaga-ku Shashin Benran (Handbook of Scientific Photography), vol.II, pp. 15-24, Maruzen Co., 1959. The emulsion used in the presentinvention may also contain stabilizers as are employed in conventionalphotographic techniques.

T he direct positive silver halide photographic emulsion used in thisinvention can be prepared by utilizing solarization, the Herscheleffect, the Clayden effect and the Sabatier effect. These effects areillustrated in, for example, C. E. K. Mees, The Theory of thePhotographic Process 2d ed. (published by Macmillan Co., 1954), chapters6 and 7. For the preparation of the direct positive silver halideemulsion utilizing solarization, it is preferred that a silver halidephotographic emulsion liable to cause solarization be prepared andpreviously subjected to uniform exposure or reaction with chemicals torender it sufiiciently developable witnout image exposure. A method ofpreparing such an emulsion is disclosed in, for instance, British443,245 and British 462,730.

The Herschel effect is caused by applying light of long wavelength tosilver halide that has been over-all subjected to exposure or reactionwith chemicals so as to be developable. In this case, a silver halideemulsion containing primarily silver chloride is favorably used, and asensitizer such as pinakryptol yellow or phenosafranine may be added topromote this effect. A method of making direct positive emulsionsutilizing the Herschel effect is disclosed in, for instance, British667,206, U.S. 2,857,273, etc.

In order to obtain a direct positive utilizing the Clayden effect, it isnecessary to expose the total surface at a relatively low intensity ofillumination after image exposure at a high intensity of illumination.This must occur in a short time, and no developable property is broughtto an area where image exposure at a high intensity of illumination isnot given before over-all exposure.

The Sabatier effect is due to the developable possibility resulting onan imagewise exposure-free area by imagewise exposing a silver halideemulsion and then subjecting it to over-all exposure in the immersedstate in a developer, or else subjecting it to reaction with chemicals.Both the effects can readily and practically be obtained in silverhalide emulsions that have a tendency to yield centers of development intheir inner portion, rather than in the surface portion of the silverhalide grains.

Methods of making such an emulsion (tending to form internal centers ofdevelopment) are disclosed in, for example, U.S. Pat. 2,592,250, U.S.Pat. 2,497,876, British Pat. 1,011,062 and German Pat. 1,207,791, etc.

The above described photographic emulsion consists of a system whereinsilver halide particles are dispersed in a solution of a high molecularweight compound. As the high molecular weight compound, gelatin isgenerally used, but synthetic high molecular weight compounds such aspolyvinyl alcohol, polyvinylpyrrolidone and polyacrylamide or naturalhigh molecular weight derivatives such as carboxymethyl cellulose,cellulose oxyethyl ether and dextran may be used alone or together withgelatin (cf. F. Evva, Zeitschrift fur Wissenschaftliche Photogtaphie,Photophysik und Photochemie vol. 52, pp. 1-24 (1957) The term activemethylene compound and derivative thereof used in this invention means acompound represented by the following General Formula 1, tautomericcompounds and metal complex salts thereof,

in which A and B are electron attractive groups and R is hydrogen atom,alkyl group, substituted alkyl group, acyl group or phenyl group.

5 6 In the above mentioned compound, compounds repre- (6) H sented bythe following General Formulas (a), (b) and I are preferable. N

General Formula (a) R l t 5 R1 5H R;

c o-methyl-acetoacetanlllde X A in which R and R are alkyl groups,substituted alkyl H 0 CH 00,115 g). oups or phenyl groups, R is ahydrogen atom, an alkyl or substituted alkyl group and R may form a ringwith g H R2 or R3- 0 General Formula (b) ethyl a-methylacetoacetate R A(s) omit- E /Y RI mo H OCH 0 0 0 o it l or ll ii ll 0 R1 in which R ishydrogen atom or alkyl group, R is an ethyl a'nhexyl'acetoacemte alkylgroup, substituted aromatic ring or sodium, R is (9) ON hydrogen atom,alkyl, substituted alkyl, cyano group or H O 4 00 H chlorine atom, R andR forming a ring in some cases, a 2 R is an aromatic ring when X is NH-and an acyl C H or alkyl group when X is --O--, X is O, NH or g 0 Hethyl a'eyanoacetoacetate NN Q (1 on,

General Formula (c) ethyl fl'acetoxycrotonate NC\ /R1 (1 H CH CH: OCzHB1 in which R is hydrogen atom, acyl or phenyl group and NH 0 R is anethoxycarbonyl or cyano group. 0

Illustrative of the compounds of the invention represented by theforegoing General Formulas (a), (b) and (c) are the following:

(1) HaC\ /CE: Ha ethyl 3-anlllnocrotonate C Q (12) CE /0 0 H; ll ll HQ 0acetylacetone (3,1154) 4) 2 0 ethyl fl-ethoxyacrylate CH: CH, /o0,H,

5 ethyl B-lminobutyrate 1,3-eyc1ohexanedione 5 (14) H 6 0H, OCH; 3

H30 0 C g l OH: OC acetoncetaldehyde dlmethyl acetal N 0 CN 6-acetyl-3methyl-2-cyc1ohexene-1-oue malononltrlle H30 c s 1:0 I 5 /OC,H E 5 NC CC C i) g 15 ethyl a-phenyl-cyanoacetate 8-aeety1-2,6-heptanedlone (17) EE (5) H3C\ /Cg2 /OC:H& C (I? C r v 0 l l N1};

ethyl nickel acetoacetate I 7 ethyl nickel acetoacetate ethyla-n-butylacetoacetate C ll acetoacetanlllde (20) I? I? C C benzoylacetone 0 C E E methyl acetoacetate CH; {I 00 E;

ethyl a-n umyl-acetoacetate CH1 OCHZ C H: 0 Na sodium acetoacetateOH,CH,

II I

2-acetylhutyrolactone 0 H3 0 CZHE II ll 0 O ethyl a-chloroacetoacetntephenylhydrazone dehydroacetate precipitate being recrystallized in.tetrahydrofuran to give a product having the following propert1es:

Melting point: l99-202 C. Ultraviolet absorption spectrum 7\max.99%EtOH: 245 mp, log e: 4.01 )rmax 99% EoOH: 352 mp, log 62 3.60Infrared absorption spectrum ycoc.: 1250 cm.- 'yNI-I: 3405 cm.- 3360cm.-

Moreover, these compounds can be used as a metal complex salt. In thiscase, the compound may be isolated as a metal complex salt, or a complexsalt may be formed in the solution by adding a metal salt thereto. Thestability constants of these metal complex salts, in particular, of thecomplex salts of acetylacetone derivatives are well known (cf. Martelland Calvin, Chemistry of the Metal Chel'ate Compounds published byPrentice-Hall Inc. (1962), in particular, table in p. 549).

The use of a silver halide in the form of a photographic emulsion in theinvention serves to enlarge the differences of reactivities between anarea irradiated with electromagnetic waves or particle rays and an areanot irradiated, that is, it enlarges the selectivity of reaction.

It has been recently reported that an active methylene compound can beused for the initiation of polymerization (cf. H. Bredereck, B.Foeh'lisch and R. Franz, Makromoleculare Chemie 92 (1966), pp. 70-90).

According to their report, the active methylene compound may initiatepolymerization of a vinyl compound in the presence of Cu++, Cland oxygenor a peroxide. In their system, however, oxygen, Cu++ or peroxide actsas an oxidizer and, consequently, the polymerization has no selectivityto irradiation.

It has also been reported that a complex compound of fi-diketone such asacetylacetone may be used as a polymerization initiator (cf. C. H.Bamford & D'. J. Lind, Chemistry and Industry 1627 (1965) and thereferences cited therein). In this report, they estimate thatpolymerization is initiated by the following radical:

In the system of this initiator, reaction is also due to the radicalgenerated by oxidation with a metal salt, and is therefore independentof irradiation.

In the present invention, on the other hand, a silver halide acts as anoxidizer, so that the rapidity of the initiation of polymerizationvaries with the presence or absence of centers of development on thesilver halide particles; that is, with the presence or absence ofirradiation with electromagnetic waves or particle rays. This is a veryimportant feature. The reaction mechanism is not yet clear in exactlyhow a silver halide is reduced with the compound of the foregoingGeneral Formulas (a), (b) or (c), resulting in a polymerization of avinyl compound. However, it is believed that the polymerizationprogresses by a radical mechanism from the fact that monomerssusceptible to radical polymerization can generally be utilized, andthat reaction proceeds in an aqueous solution and is retarded by aradical polymerization inhibitor. It is not clear whether the radical isgenerated directly by the reaction of the compound of the foregoingGeneral Formulas (a), (b) or (c) with a silver halide, or by interactionwith water, oxygen, etc. in the system, but it is clear that thepolymerization of a vinyl compound occurs simultaneously wtih thereduction of the silver halide, since there is found no polymerizationin the case of adding the vinyl compound to the reaction system afterthe irradiated silver halide is reduced with the compound of theforegoing General Formulas (a), (b) or Therefore, an intermediateproduct of a silver halide and compound of the General 'Formulas (a),(b), or (c) may possibly contribute to the polymerization reaction.

For a report on the intermediate product formed by the oxidation ofB-diketone or fl-ketoacid ester with a monoelectron oxidizer, ceriumsulfate, one should refer to G. A. Russel & Lockengard, Journal of theAmerican Chemical Society 89 5059 (1967).

In their report, some discussion is made on the intermediate product, atthe radical state, the following reaction scheme is considered for theoxidation process of 1,3- cyclOpentanedione:

The initiation of polymerization in the present invention is likely dueto the radicals of active methylene compounds formed during oxidation ofa silver halide. Upon stopping the reaction in a suitable period oftime, there is selectively formed a high molecular weight compound atthe irradiated areas only, and, when a longer reaction time was used,the formation thereof begins at the nonirradiated areas. However, theutility of the invention is not spoiled by this phenomenon, whichcorresponds to the so-called fog phenomenon in ordinary photographywherein exposed and non-exposed areas are all blackened by increaseddeveloping time.

According to the so-called tanning developing method, crosslinkinggelatin with an oxidation product of a developing agent, which method iswell known as a method for forming an image with a high molecular weightmaterial by utilizing the photosensitivity of a silver halide, theformed image is limited to a substance of crosslinked gelatin. On thecontrary, images of high molecular weight material obtained according tothe present invention show various excellent properties depending on thevinyl compounds used, some of the properties, for instance dyeingproperty and chemical resistance, being better than those of crosslinkedgelatin.

It is found that, according to the method of this invention, thepolymerization of a vinyl compound is accelerated by the presence ofsulfite ion in the system.

The sulfite ion may be supplied to the system either by adding acompound possessing sulfite ions 'such as alkali metal and ammoniumsulfites and bisulfites, or by adding a material capable of formingsulfite ions through hydrolysis in aqueous solution, such as alkalimetal and ammonium pyrosulfites, and adducts of bisulfite and aldehydessuch as formaldehyde or glyoxal. Although the appropriate amount ofsulfite ion to be added to the'system depends on the kind and amount ofreducing agent and vinyl monomer employed and the pH of the system, itis preferably 0.05 mol or more per 1 l. of the system, particularly 0.2mol or more.

The addition of a sulfite to a photographic developer is widely known.In this case, it is believed that the sulfite plays the role ofinhibiting the autooxidation of a developing agent such as hydroquinoneor p-aminophenol through reaction with an oxidized product thereof, aswell as inhibiting any uneven developing reaction (cf. C. E. K. Mees,The Theory of the Photographic Process 2d ed., published by MacMillanCo. (1954), p. 652). It is now to be noted that the polymerizationaccelerating effect of a sulfite in the present invention is completelydifferent from the action of removing an oxidized product in theordinary developer as mentioned above, since, in this invention anoxidized intermediate product of an active methylene compound with asilver halide initiates the polymerization. If the sulfite herein servedonly to remove the oxidized product, polymerization would be suppressedrather than enhanced.

Although the mechanism of the sulfite action in this invention is notclear, it is reasonable to think that the hindrance of polymerization byoxygen is inhibited.

Suitable for use as the vinyl compound of the invention areaddition-polymerizable compounds which are liquid or solid at roomtemperature or mixtures thereof, for example, acrylamide, acrylonitrile,N-hydroxy-methylacrylamide, methacrylic acid, acrylic acid, calciumacrylate, sodium acrylate, methyl methacrylate, methyl acrylate, ethylacrylate, vinylpyrrolidone, Z-Vinylpyridine, 4-vinylpyridine,2-methyl-N-vinylimidazole, potassium vinylbenzenesulfonate andvinylcarbazole. In the invention, a compound having two or more vinylgroups is particularly suitable, and this may be used alone, or togetherwith the foregoing compound having one vnyl group. Illustrative of suchcompounds having two or more vinyl groups areN,N-methylenebisacrylamide, ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate, triethylene glycol dimethacrylate, polyethyleneglycol dimethacrylate, divinyl ethers and divinyl benzene.

In the present invention, a water-soluble vinyl compound is preferablyused, but a water-insoluble vinyl compound may be polymerized in theform of an emulsion. The emulsification may be carried out by a suitablestirring device in the presence of a surfactant and/ or high molecularweight compound in the conventional manner.

Any electromagnetic wave or corpuscular ray to which the ordinaryphotographic emulsion is sensitive can be used in this inveniton. Thatis to say, visible rays, ultraviolet rays, infrared rays of 1.3 micronsor less, X-rays, -rays and corpuscular rays such as electron rays andarays are available.

For the practice of the invention, it is necessary to conduct two stepsof irradiation with electromagnetic waves or particle rays in thereduction and polymerization reaction. In particular, for the recordingof an image, it is desired that there be very little positional movementof silver halide particles in the reaction system between radiation withelectromagnetic waves or particle rays and the polymerization reaction.For this purpose, the system is preferably held in the state of a highlyviscous liquid or gel. A photographic emulsion, to which natural orsynthetic high molecular weight compounds have previously been addeditself has some viscosity or else can be gelled to some extent, but whenthis is insufiicient, larger amounts of a high molecular weight compoundmust further be added.

When subjected to irradiation with electromagnetic waves or particlerays, a silver halide may be either in an aqueous solution or in the gelstate. That is to say, a highly viscous or gelled photographic emulsionmay be used on a suitable support in the undried state, or may be coatedonto a suitable support in the dried state. Since the reduction andpolymerization occur simultaneously, the reduction must be carried outin the presence of a vinyl compound. In the method of this invention,both the foregoing active methylene compound acting as a reducing agentfor the silver halide and the vinyl compound to be polymerized maypreviously be contained in the emulsion, or only one may be containedtherein while the other may be added to the system after irradiation. Insome cases, both may even be added after irradiation.

Since the presence of water is necessary for the practice of thereduction and polymerization reaction, the reaction must be carried outin an aqueous solution or in the wet gelled state.

This reaction proceeds well in an alkaline state, i.e. at a pH greaterthan about 6, preferably greater than about 7, the most suitable pHdepending upon the variety and concentration of the silver halide,reducing agent and high molecular weight compound as the medium, and thereaction temperature.

In the case where a photographic emulsion is coated onto a support andused as a photographic light-sensitive material, this light-sensitivematerial is irradiated with electromagnetic waves or particle rays andimmersed in an aqueous alkali solution to cause the reaction to proceed.The reducing agent or vinyl compound can be contained in this solution.

Stopping the reaction can readily be accomplished by converting thesystem to an acid range, for example, a pH of less than 5, removing thereactant by Washing, cooling, dissolving any silver halide in a fixingsolution for photography, or adding a polymerization inhibitor to thesystem.

Where a high molecular weight material as a medium for the silver halideand a vinyl compound monomer are previously formed in a coating, it isdesirable to add a small amount of inhibitor for thermal polymerizationin order to inhibit spontaneous overall thermal polymerization of thevinyl compound prior to processing. As the inhibitor for thermalpolymerization for ordinary radical polymerization, for example, thereare p-methoxyphenol, hydroquinone, alkylhydroquinone and2,6-di-t-butyl-pcresol.

Where a vinyl compound has previously been incorporated into the system,the weight of the vinyl compound used is -30 times, preferably %4 timesas much as that of a high molecular weight compound previously added.The silver halide used is 1 -2 times, preferably /2 times as much as thehigh molecular weight compound previously added. All figures are byweight. In the case of previously adding a reducing agent to the system,also, the amount of a reducing agent is preferably about mols per 1 molof a silver halide used. Moreover, in the case of adding an inhibitorfor thermal polymerization, its amount is preferably A times by weight,as much as that of the vinyl compound. In the case of adding a vinylcompound to a processing solution, it is ordinarily desired that theconcentration be as high as possible and that the amount added to thesolution be limited only by the solubility of the vinyl compound in theprocessing solution. In the case of adding an active methylene compoundused as a reducing agent to a processing solution, the concentration ispreferably 4 mols, particularly 1 mol.

Further to the above, there may be a suitable interval of time betweenthe irradiation with electromagnetic waves or corpuscular rays and thepolymerization, as in ordinary silver halide photography. In some cases,the effect of radiation decreases, depending on the properties of aphotographic emulsion used, and the conditions and time the photographicmaterial is allowed to stand. In such cases, desirable effects can beobtained by increasing the amount of exposure.

Where the method of this invention is adapted for the recording of animage, it is possible to optionally utilize the differences between avinyl compound and its polymer in their physical and chemicalproperties, such as solubility, light scattering, adhesiveness, dyeingaffinity, etc. In utilizing the difference of solubility, for example,an image can be formed by dissolving off a non-polymerized area afterradiation and reaction, thus leaving an image of high molecular Weightmaterial on the irradiated area only.

In this case, it is preferred that a high molecular weight compoundwhich is added initially me dissolved off together with the non-reactedmonomer. To this end, preferably, the high molecular weight compoundcontained initially in the system is such a high molecular weightcompound that the structure is two-dimensional or linear, andsubstantially free from cross-linking, or else the main chain orcross-linking can readily be broken, while the high molecular weightcompound formed by the reaction is a so-called three-dimensionalcross-linked polymer. For this purpose, it is desired, as mentionedbefore, to use a compound having a plurality of vinyl groups alone, ortogether with a compound having one vinyl group. However, even if thehigh molecular weight material formed is a twodimensional high molecularweight material, there often occurs a difference in solubility betweenan area where the high molecular weight material and a high molecularweight compound added previously are brought into interaction with eachother to form a high molecular weight material, and another area wheresuch a high molecular weight material is not formed, for example, in acase of polyacrylic acid and gelatin. Thus, it is not always necessaryto use a monomer having a plurality of vinyl groups.

An image consisting of the high molecular weight material made by themethod of this invention can be utilized for various printing andrecording methods.

Furthermore, the present invention is available for forming a dye image.In this method, a polymer image is selectively dyed with a dye having anopposite charge by using a monomer having a group which is capable ofhaving imparted thereto a charge by ionization or by adding thereto ahydrogen cation, such as a vinyl monomer and then forming a polymercapable of having a charge imparted thereto by ionization or by theaddition of hydrogen cation. The dye image thus obtained can betransferred to another support by various state of the art methods.

Addition-polymerizable vinyl compounds capable of having a chargeimparted thereto by ionization or by the addition of a hydrogen cation,which can be utilized in the above-mentioned case, are the following. Asthose providing a high molecular weight compound which is to be formedwith negative charge, there are: vinyl compounds having a carboxyl groupsuch as acrylic acid, methacrylic acid, itaconic acid and maleic acid;vinyl compounds having a metal or ammonium carboxylate group such asammonium acrylate, sodium acrylate, potassium acrylate, calciumacrylate, magnesium acrylate, zinc acrylate, cadmium acrylate, sodiummethacrylate, calcium methacrylate, magnesium methacrylate, zincmethacrylate, cadmium methacrylate, sodium itaconate and sodium maleate;vinyl compounds having sulfonate group such as vinylsulfonic acid andp-vinylbenzenesulfonic acid, and vinyl compounds having a metal orammonium sulfonate group such as ammonium vinylsulfonate, sodiumvinylsulfonate, potassium vinylsulfonate and potassiump-vinyl-benzenesulfonate. As materials providing a high molecular weightcompound formed with a positive charge, there are vinyl compounds havinga basic nitrogen atom such as 2-vinylpyridine, 4-vinylpyridine,5-vinyl-2-methylpyridine, N,N- dimethylaminoethyl acrylate,N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate andN,N- diethylaminoethyl methacrylate and vinyl compounds having aquaternary nitrogen atom made by reacting these bases with methylchloride, ethyl bromide, dimethyl sulfate, diethyl sulfate and methylp-toluenesulfonate. These compounds are commercially sold and may besynthesized by any well-known method. These compounds may be used aloneor in combination. Moreover, they may be used together with acharge-free water-soluble, additionpolymerizable vinyl compound such asacrylamide, N-

hydroxymethylacrylamide, methacrylamide, methyl methacrylate,vinylpyrrolidone, N,N-methylene-bisacrylamide, triethylene glycoldimethacrylate and triethylene glycol dimethacrylate. In the case ofusing a vinyl compound having no charge, the reactivity and theporportion of the vinyl compound must be so selected that a highmolecular weight compound having substantially no electrolyticallydissociating groups is formed as a result of the polymerization of onlythe vinyl compound having no charge.

As a dye capable of ionizing and carrying a charge, in this case therecan be used oridinary acid dyes and basic dyes. When using a vinylcompound such as providing a high molecular weight compound having anegative charge, a basic dye is used. An acid dye whose dye molecule isnegatively charged dyes a high molecular weight compound having positivecharge well, while a basic dye whose dye molecule is positively chargeddyes a high molecular weight compound having negative charge well.Therefore, a dye image will be obtained which corresponds to a highmolecular weight compound which has been imagewise formed.

Where gelatin is used as a binding agent for a photographic emulsion,dyeing must be carried out with a consideration of the isoelectric pointof gelatin, since gelatin is an amphoteric electrolyte. At a pH higherthan the isoelectric point of the gelatin used, the gelatin has negativecharge and, at a lower pH, a positive charge.

In the case where there is formed a high molecular weight compound(hereinafter a high molecular compound) having a negative charge,therefore, dyeing is carried out with a basic dye at a pH lower than theisoelectric point of gelatin, whereby only the high molecular image canbe dyed without gelatin being dyed therewith. Or, alternatively, thedyeing is initially carried out uniformly at a pH of higher than theisoelectric point, followed by washing with a washing solution having apH lower than the isoclectric point of gelatin, whereby a high molecularimage free area is washed out, and only the high molecular image arearemains colored.

In the case where a high molecular image having a positive charge isdyed with an acid dye, similarly dyeing may be carried out at a pHhigher than the isoelectric point of gelatin. If the pH is too high ortoo low, the solubility of a dye lowers or else the ionization of thehigh molecular compound to be charged is disturbed. Accordingly, themost suitable range for the pH is determined according to the variety ofvinyl compound, dye and binder, such as gelatin, used. A preferred pHrange is 2.5-4.5 where a gelatin having an isoelectric point of about4.9, processed ordinarily with lime, is used and a high molecularcompound having negative charge is dyed with a basic dye, and 5.0-8.0where a high molecular compound having positive charge is dye with anacid dye. Dyes available are, as the acid dye, C.I. Acid Yellow 7 (C.I.56205), C.I. Acid Yellow 23 (C.I. 19140), C.I. Acid Red 1 (C.I. 18050),C.I. Acid Red 52 (C.I. 45100), C.I. Blue 9 (C.I. 42090), C.I. Acid Blue45, C.I. Acid Blue 62 (C.I. 62045) and C.I. Acid Violet 7 (C.I. 18055),and, as the basic dye, C.I. Basic Yellow 1 (C.I. 49005), C.I. BasicYellow 2 (C.I. 41000), C.I. Basic Red 1 (C.I. 45160), C.I. Basic Red 2(C.I. 50240), C.I. Basic Blue 25 (C.I. 52025), C.I. Basic Violet 3 (C.I.42555) and C.I. Basic Violet (C.I. 45170), etc. The number of these dyesis according to the Color Index (2nd Ed.) and they are sold undervarious brand names.

For the practice of this method, it is necessary to effect the reductionand polymerization reaction and then dyeing after irradiation withelectromagnetic waves or particle rays.

When only non-polymerized vinyl monomer is washed out after irradiation,reduction and polymerization, an image from a highly polymerizedcompound is left. Since the polymer is generally less soluble than themonomer and scarcely diffuses in a gelatin layer where a high molecularcompound has been added initially as a binder for a silver halidephotographic emulsion, it is not dissolved in water and retained likegelatin, only a polymerized area 14 is left to form an image. The use ofa monomer having two or more vinyl groups may strengthen theinsolubility and undiffusibility of the polymer.

The dyeing mentioned above (after polymerization) yields a dye imagebonded with a high molecular image. This dye image can be utilized as aclear dye image by removing silver halide by fixing and reacting with anoxidizer and a solvent for silver salts to dissolve oif the silverimage. When a reducing agent having a very high polymerizationinitiating effect is employed, the polymerization reaction occurssufficiently even when only a very slight amount of reduced silver isformed; hence, in such a case, it is scarcely, or not at all, necessaryto remove the silver images by oxidation.

The formed dye image may be transferred to another support. Transferringcan be carried out by wetting a layer possessing the formed dye imagewith a solvent for the dye such as methanol, water or an aqueoussolution of acid, base or salt, and bringing the wetted layer into closecontact with the support which it is to be transferred to. As a supportto be transferred to, there can be used ordinary papers, papers ontowhich a hydrophilic polymer layer or gelatin layer has been coated, andfilms onto which a hydrophilic polymer or gelatin layer has been coated.In transferring to a support onto which a gelatin layer has been coated,one which has been mordanttreated, for instance with an aluminum salt,is preferably used as in ordinary dye transfer methods. Once a highmolecular image capable of being charged is made, it can be reproduced aplurality of times by dyeing and transferring as mentioned above. Onedyeing can give several transfer images, and one high molecular imagecan be subjected to repeated dyeing to readily give a number of copies.

The present invention will be further illustrated by the followingnon-limiting examples.

EXAMPLE 1 A gelatino-silver chlorobromide photographic emulsioncontaining silver chlorobromide corresponding to 42 g. of silver andhaving a molar ratio of 7:3, containing 60 g. of gelatin, having a pH of5.8, pAg of 7.6, and a fine particle size, was divided into twoportions. One portion was exposed to a fluorescent lamp. For exposure,200 ml. of the emulsion liquid at about 35 C. was spread in a vat of 20cm. x 25 cm. and allowed to stand under agitation for about 5 minutesunder an illumination of about 300 lux. 2.5 ml. of the exposed emulsionand the non-exposed emulsion were, respectively, taken and placed intotest tubes of 1.6 cm. in diameter, to which 6 ml. of water, 4.0 g. ofacrylamide and 10- mol of acetylacetone were added. After adequatelystirring and adjusting the temperature to 60 C., the test tubes wereallowed to stand in a heat insulating material of foamed polystyrene of2 cm. thickness, kept in a thermostat at 60 C., 3 ml. of 1 N sodiumhydroxide was directly added to both test tubes and the change intemperature was recorded by a thermistor. -In the system formed from theexposed emulsion, the acrylamide was polymerized and the temperature wasraised by the heat of polymerization, the temperature of the systemreaching 108 C. after about 20 minutes from the initiation of reaction.In the system from the non-exposed emulsion, the temperature reachedonly 78 C. in the same reaction time.

In the above, it is evident from the generation of heat thatpolymerization occurred. Although heat may be generated by the reductionof the silver halide in addition to the polymerization reaction, it istoo little to be detected as a change of temperature by the instrumentused in this example. When using hydroquinone in place of acetylacetone,for example, silver halide was reduced to be black silver, but nogeneration of heat was detected.

In the case of using the non-exposed emulsion, polymerization occurswith generation of heat if the reaction time is lengthened. Thiscorresponds to the general phenomenon found in ordinary photographicemulsion, i.e. if the developing time is too long, silver halide atnon-exposed areas is also reduced to give fog and the image will hardlybe detectable. Accordingly, the utility of the photographic material ofthis invention is not spoiled by this phenomenon.

EXAMPLE 2 The same procedure as that of Example 1 was repeated at thesame conditions except that an active methylene compound as shown in thefirst line of Table 1 was used in place of acetylacetone, and thequantity of sodium hydroxide was changed. The amount of the activemethylene compound is shown in Table 1, second line, the temperature ofthe thermostat in the third line, the amount of l N sodium hydroxide inthe fourth line, the time to reach maximum temperature in the systemusing the exposed emulsion in the fifth line, the temperature at thattime in the sixth line and the temperature of the system using thenon-exposed emulsion at the same time in the seventh line.

In any case, polymerization occurred preferentially with the exposedemulsion.

After being allowed to stand at C. for five minutes, a light brown imageappeared at the exposed area. The sample was washed with a 1.5% aqueoussolution of acetic acid for seconds and fixed with the following fixingsolution.

G. Sodium thiosulfate (anhydrous) 150 Potassium metabisulfite 15 Waterto make 1000 ml.

The fixed and water-washed sample was immersed in a 0.1% aqueoussolution of a red basic dye, Rhodamine 6 GCP (C.I. Basic Red 1), at roomtemperature for five minutes, and then washed with a 5% aqueous solutionof acetic acid for five minutes. The dye on the area other than theforegoing brown image area was Washed out, but the image area whichremained was colored red. The brown image, a silver image, could readilybe dissolved off with Farmers reducing solution. Upon removing thesilver image, a clear red image was obtained. By reversing the order ofdyeing and removal of the silver image, i.e., by removing the silverimage first to give an apparently colorless and transparent image andthen dyeing as mentioned above, a clear red image could similarly beobtained.

TABLE 1 Bath Temp. of Temp. 01 Amount, temp., Amount of Time, exposednon-exposed Number Reducing agent mg. O IN NaOH min. emulsion emulsion177 2 30 75 54 162 3 58 99. 5 86 116 57 3 27 78 70 200 57 3 30 63.5 57124 58 3 54 69. 5 62 B-Acetoxycrotonate 172 57 0.5 150 60 59 25Ethyl-2-chloroacetoacetate 165 58 1.0 20 107 83 26 Phenylhydrazonedehydroacetate 258 55 1.0 38 80 71. 5

EXAMPLE 3 The dye image thus obtained could be transferred to a Aphotographic film coated with a gelatino-silver chloroiodobromidephotographic emulsion was exposed and then treated with a solutioncontaining ethyl aphenyl-eyanoacetate (No. 16) and sodium methacrylateto effect imagewise polymerization. The thus obtained polymer image wasdyed with a basic dye. The photographic film was made by under-coatingboth surfaces of a support of polyethylene terephthalate, applying anantihalation layer to one surface, applying to the other surface a finegrain gelatino-silver halide emulsion containing 0.7 mol of chlorine,0.3 mol of bromine and 0.001 mol of iodine per 1 mol of silver and 100g. of gelatin, to which was added merocyanine sensitizing dye having amaximum sensitivity at 550 III/1., 1.5 g. of mucochloric acid per 100 g.of gelatin as a hardener, and suitable stabilizers and surface activeagents. 50 mg. of silver were contained per 100 cm. in the coating, andthere was then applied thereto a protective layer of gelatin of about0.8;/. onto the emulsion layer. This photographic film is normally usedfor making line and half-tone images for photomechanical reproduction.

A line image negative was superposed on the photographic film, exposedto a light of about 100 lux for 2 seconds and immersed in a solutionhaving the following composition under a red safety light.

Sodium methacrylate g 75 Ethyl a-phenylcyanoacetate (No. 16) g- 8.5Water ..ml 75 2 N-NaOH, to adjust pH to 11.6.

sheet of paper, for example, by wetting a writing paper with methanol byrubbing it with a sponge containing methanol, contacting the dye imageclosely with writing paper under pressure, and separating both afterabout 30 seconds.

When using a 0.1% aqueous solution of Crystal Violet (C.I. Basic Violet3) for the dyeing, forming a dye image and transferring were similarlycarried out to obtain a blue-violet transfer image.

When using a 0.1% aqueous solution of Auramine 0- 100 (CI. Basic Yellow2) as a dye, a yellow image was obtained.

When using a 0.1% aqueous solution of Basic Blue G.O. (C.I. Basic Blue25) as a dye, a blue image was obtained.

In transferring a dye image, it is not necessary to remove the silverimage and the silver halide. Accordingly, a transferred image was alsoobtained by dyeing and transferring directly after developing,polymerizing, stopping and washing with water.

EXAMPLE 4 The same film as that of Example 3 was exposed as in Example 3and processed with various solutions having the following formulas, andcontaining various reducing agents as shown in Table 2.

Sodium methacrylate g.

Reducing agent Shown in Table 2.

Water 75 ml.

2 N NaOH To adjust pH to the value shown in Table 2.

18 The sample was processed at 30 C. for a period of oped andpolymerized. Using a basic monomer, a polytime as shown in Table 2,fixed and washed with water mer capable of being dyed with an acid dyewas given.

as in Example 3 and then dyed with 0.1% Rhodamine 6 ll-2,3,-d' th 1' 'dli GCP as in Example 3. The transmission densities for 5 vmy lme yum azoum p-toluenesulfonate 75 g. green light before and after dyeing weremeasured for Ethyl a pheny1cyanoac6tate (Na exposed areas andnon-exposed areas of each sample. 16) 5 g.

The n of reducing agent, amount, P Value durlhg Potassium metabisulfiteRequired for adjustprocessing, processing time, optical density beforedyeing i H t 9 11 5 and optical density after dyeing-are tabulated inTable 2. 10 Water 85 ml.

. TABLE 2 Density of non- Density of exposed area exposed areaProcessing time, Before After Before After Number Reducing agent Amount,g. min. dyeing dyeing dyeing dyeing pH 1 Acetylacetone 5.00 70 0.07 0.270.11 0.70 11.60 2 1,3eyclohexaned1one 5. 04 30 0.08 0.44 0.11 2.20 11.50 fi-aeetyl-3-methyl-2-cyelohexene-1-one 6. 84 10 0.18 0.35 0.33 1.5211. 50 3-acetyl-2,6-heptadione 7. 70 0.09 0.20 0.10 0.35 11.50 5.85 700.08 0.29 0.08 0.76 12.40 0.32 70 0. 09 0.25 0.08 0.38 11. 50 6.48 700.08 0.18 0.08 0.40 11.50 9. 53 70 0.08 0.19 0.08 0.25 11. 50 6.97 70 0.07 0.17 0. 05 0.22 11. 50 7.74 70 0. 07 0. 22 0.08 0. 84 11.50 9.22 700.11 0.17 0.12 0.25 11.50 5.40 70 0. 09 0.17 0. 09 0.22 11. 00 5.85 700.17 0. 34 0.08 2.00 11. 50 14-- Acetylaeetaldehyde dimethyl acet 5. 9470 0.10 0. 19 0. 0.23 9. 00 15 Malonorlitrile 2. 97 O. 08 0. 23 0. 09 2.42 9. 00 16 Ethyl a-phenyl eyanoaeetate 8.50 5 0.09 0.26 0.29 1.51 11.6017 Ni-ethylaeetoaeet e 1.17 60 0.08 0.28 0. 00 1.48 11.50 Ethyla-butylacetoacetate 8-37 64 0.07 0.17 0.08 0.95 11.60

In a cases, the sity ue to dyeing increased more l-vinyl 2,3dimethyimidazolium p toluenesulfonate at an exposed area than on annon-exposed area. This 30 having a melting point of 142.5 C. wasobtained by reshows that the exposed area was selectively dyed. Thls isacting 1-vinyl-2-methylimidazole with methyl p-tolueneal o supported bythe fact that the silver lmage of each sulfonate at room temperature andrecrystallizing the sample was removed by Farmers reducer to leave aclear product f o th nol nd th red image- In a sample wlth a 10W sliverImage y, a The sample was processed at 30 c. for 30 minutes to Clear redimage found even WIT-bout lemovlng the thus obtain a light brown silverimage together with an silver image. These dye images could betransferred to image of a polymer of a quaternary salt. That is to say,iti paper using methanol slmilar to Example 3. the sample was fixed andwashed with water as in Ex- EXAMPLE 5 I ample 3, dyed with 0.1% aqueoussolution of blue acid dye, Suminol Leveling Sky Blue R extra conc. (C.I.Acid Blue 62) and washed with a 1% sodium hydrogen carbonate solutionfor five minutes to give a blue image. It was confirmed that, in thecase of a higher pH of the system, the sharpness of an image by dyeingwas larger and the polymerization reaction proceeded to a greater Thisexperiment is similar to Example 4, was carried out using a metal saltin combination with the active methylene compound. As a reducing agent,phenylhydrazone dehydroacetate was used with a metal salt to determinethe efliect thereof. The sample was immersed in the following processingsolution degree. When the sample was subjected to desilvering asPotassium metabisulfite 3 g. in Example 3, a sharp blue image wasobtained. The Sodium methacrylate 75 2. image could be transferred to awriting paper wetted with Phenylhydrazone dehydroacetate 12 g. methanolas in Example 3. When a dye transfer paper Metal Salt X (prepared bycoating a baryta paper with a gelatin layer Water 75 of about 10 micronsthickness, then immersing it in an 2 NN T0 adlustfhe P as aqueoussolution of alum and drying) was wetted with S110WI11I1Tab1e3- water,brought into close contact with the foregoing dye The sample wasprocessed at a temperature for a period ag allowed to stand for oneminute and then sepaof time as shown in Table 3, and the results aretabulated rated, a high density sharp blue image was obtained. TheinTable 3 as in Example 4. sample was immersed in 0.1% aqueous solutionof red TABLE 3 Density of non- Density of exposed area exposed area TBefore After Beiore After Metal salt pH $1 1. dyeing dyeing dyeingdyelng None 9.10 40 30 0.08 0.20 0.09 1.30 40 40 30 0. 16 0. 27 0. 57 3.47 i t tiiifr n iii ii if; a0 40 a0 0. 07 0. 34 0.18 2.07 Copper acetate9.20 40 30 0. 22 1.98 0.97 over4 As is evident fr m Table the imagedensity due f acid dye, Solar Rhodamine B extra (Cl. Acid Red 52) dyeingwas raised by the use of a metal salt. This is POSSI- which was used inplace of Suminol Leveling Sky Blue R y due to the fact that the reducingagent and metal salt eXtra conc. Immersion was for five minutes foroverall are partly chelated to change the reactivity of the active d i di was h i d i Koltoff b ff r 1 methylene compound, or else that themetal salt catalyzes tion at pH 5.0 for three minutes and washed withwater, the redox reaction of the silver halide with the reducing th b ii a Sample Where the image area was only agent. The correct mechanismthereof is not completely dyed red. I clear. The image could betransferred to a writing paper EXAMPLE moistened with methanol and to atransfer paper moist- The film of Example 3 was exposed as in Example 3,ened with water as mentioned above.

processed with a solution of the following recipe, devel- The sample wasdyed with Solar Pure Yellow 8 G 19 (Cl. Acid Yellow 7) and Washed with abuffer solution of pH 5.0 to give a yellow image which could betransferred to a writing paper wetted with methanol, or a transfer paperwetted with water, by pressing.

In this invention, the number of carbon atoms in an alkyl or substitutedalkyl group is preferably less than 17. Acceptable substituents for thesubstituted alkyl groups are carbonyl, ester, halide, carboxylic acid,etc.

Rings which R; can form with R or R include 6 membered rings ofsaturated or unsaturated carbons or -6 membered heterocyclic ringsincluding nitrogen or oxygen. Representative substituents forsubstituted aro matic rings include mtoxy, halide, nitro, acyl,carboxyl, sulfone and hydroxyl groups.

Finally, by the term high molecular weight material is meant a materialwith a molecular weight greater than 1,500, with 10,000 being a morepreferred figure.

We claim:

1. A method for forming a polymer image from a re action systemconsisting essentially of a silver halide emulsion, an active methylcompound, and at least one addition-polymerizable vinyl monomer orvinylidene monomer which comprises developing a silver halidephotographic emulsion having a latent image with at least one activemethylene compound represented by the following General Formulas (a),(b) or (c), tautomeric isomers thereof and metal complex salts thereof,in the presence of at least one addition-polymerizable member selectedfrom the group consisting of vinyl monomers and vinylidene monomers topolymerize said monomer selectively at the latent image areas, saidsilver halide acting as an oxidizer, said polymerization being initiatedby the oxidizing intermediate product formed from the reactivity betweensaid active methylene compound and said silver halide:

Genenal Formula (a) wherein R and R are members selected from the groupconsisting of an alkyl group, a substituted alkyl group, and asubstituted phenyl group, R is a member selected from the groupconsisting of a hydrogen atom, an alkyl group and a substituted alkylgroup, said R being capable of forming a ring with R or R GeneralFormula (b) o it ll a r-R1 ll wherein R is a member selected from thegroup consisting of a hydrogen atom and an alkyl group, R is a memberselected from the group consisting of an alkyl group, a substitutedaromatic ring, and sodium, R is a member selected from the groupconsisting of a hydrogen atom, an alkyl group, a substituted alkylgroup, a cyano group and a chlorine atom, R and R capable of forming aring, R-, being an aromatic ring when X is NH- and a member selectedfrom the group consisting of an acyl group and an alkyl group when X- isO, X is a member selected from the group consisting of 0*, NH, and

and Y is a member selected from the group consisting of O and NH; and

General Formula (c) wherein R is a member selected from the groupconsisting of a hydrogen atom, an acyl group and a phenyl group, and Ris a member selected from the group consisting of an ethoxy carbonylgroup and a cyano group.

2. The method of claim 1, wherein said alkyl group and said substitutedalkyl group contain less than 17 carbon atoms.

3. The method of claim 1, wherein said substituted alkyl group issubstituted with substituents selected from the group consisting ofcarbonyl, ester, halide and carboxylic acid.

4. The method of claim 1, wherein said ring formed between R and R or Ris a ring selected from the group consisting of a. six-membered ring ofsaturated or unsaturated carbon atoms and a five to six-memberedheterocyclic ring having within its molecular nucleus 2. member selectedfrom the group consisting of nitrogen and oxygen.

5. The method of claim 1, wherein said substituted aromatic ring issubstituted with a substituent selected from the group consisting ofmethoxy, halide, nitro, acyl, carboxyl, sulphone, and hydroxyl.

6. The method of claim 1, wherein said polymerization is carried out inthe presence of a sulfite ion.

7. The method of claim 6, wherein the precursor for said sulfite ion isa members selected from the group consisting of an alkali metal sulfite,an alkali metal bisulfite, an ammonium sulfite, an ammonium bisulfite,an alkali metal pyrosulfite, an ammonium pyrosulfite, and an aldehydebisulfite adduct.

8. The method of claim 6, wherein said sulfite ion is present in anamount greater than 0.05 mol per liter.

9. The method of claim 6, wherein said sulfite ion is present in anamount greater than 0.2 mol per liter.

10. The method of claim 1, wherein an image of the formed polymer isselectively dyed with a dye having a charge opposite that of the highmolecular weight compound when ionized.

11. The method of claim 10, wherein said high molecular weight compoundis one to be formed with a negative charge and is a member selected fromthe group consisting of vinyl compounds having a carboxyl group, vinylcompounds having a metal or ammonium carboxylate group, vinyl compoundshaving a sulphonate group, and vinyl compounds having a metal orammonium sulphonate group.

12. The method of claim 10, wherein said high molecular weight compoundis formed with a positive charge and 'is a member selected from thegroup consisting of vinyl compounds having a basic nitrogen atom, andvinyl compounds having a quaternary nitrogen atom.

13. The method of claim 10, wherein said dye is a member selected fromthe group consisting of an acid dye and a basic dye.

14. The method of claim 10, wherein said silver halide photographicemulsion is a gelatin emulsion.

15. The method of claim 14, wherein a basic dye is utilized and the pHof said system is maintained lower that the iso-electric point of saidgelatin.

16. The method of claim 15, wherein said pH ranges from 2.5 to 4.5.

17. The method of claim 15, wherein said pH ranges from 5.0 to 8.0.

18. The method of claim 14 wherein said dye is an acid dye and the pH ofsaid gelatin is maintained higher than the iso-electric point of saidgelatin.

19. The method of claim 1 wherein said vinyl and vinylidene monomer haveat least two vinyl groups in their molecular structure.

20. The method of claim 19, wherein said monomer having at least twovinyl groups is a member selected from the group consisting ofN,N-methylenebisacrylamide, ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate, triethylene glycol dimethacrylate, polyethyleneglycol dimethacrylate, divinyl ether, and divinyl benzene.

21. The method of claim 1, wherein said additionpolymerizable monomer isa vinyl monomer which is water-soluble.

22. The method of claim 1, wherein said vinyl monomer is a memberselected from the group consisting of acrylamide, acrylonitrile,N-hydroXy-methacrylamide, met-hacrylic acid, acrylic acid, calciumacrylate, sodium acrylate, methylmethacrylate, methylacrylate,ethylacrylate, vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-methyl N vinylimidazole, potassium vinylbenzene sulphonate, and vinylcarblazole.

23. The method of claim 1, wherein said reaction is carried out in anaqueous system.

24. The method of claim 1, wherein said additionpolymerizable compoundis present in an amount of from to 30 times by weight the amount of highmolecular weight compound.

25. The method of claim 24, wherein said amount ranges from A to 4 timesas much as that of the high molecular weight compound.

26. The method of claim 1, wherein, said silver halide is present in anamount of from to 2 times by weight the amount of the high molecularweight compound.

27. The method of claim 26, wherein said amount ranges from to times theamount of said high molecular weight compound.

28. The method of claim 1, wherein said active methylene compound ispresent in an amount of from to 5 mols per mol of silver halide.

29. The method of claim 28, wherein said amount ranges from to 1 mol permol of silver halide.

30. The method of claim 17, further comprising the addition of a thermalpolymerization inhibitor in an amount of from i to 35 times by weight,as much as that of said vinyl compound.

31. The method of claim 30, wherein said inhibitor is a member selectedfrom the group consisting of p-methoxy phenol, hydroquinone, alkylhydroquinone and 2,6-di-tbutyl-p-cresol.

32. The method of claim 1, wherein said method is carried out at a pHgreater than 6.

33. The method of claim 1, wherein said method is carried out at a pHgreater than 7.

34. The method of claim 1, wherein said methylene compound is a memberselected from the group consisting of acetylacetone,1,3-cyclohexanedione, 6-acetyl- 3-methyl-2-cyclohexene-l-one,3-acetyl-2,6-heptanedione, ethyl acetoacetate,o-methyl-acetoacetanilide, ethyl or methylacetoacetate, ethyla-n-heXyl-acetoacetate, ethyl orcyanoacetoacetate, ethylfl-acetoxycrotonate, ethyl 3-anilinocrotane, ethyl ,3-ethoxyacrylate,ethyl B-iminobutyrate, acetoacetaldehyde dimethyl acetal, malononitrile,ethyl orphenyl-cyanoacetate, ethyl nickel acetoacetate, ethyl u-nbutylacetoacetate, acetoacetanilide, benzoyl acetone, methyl acetoacetate,ethyl a-n-amyl-acetoacetate, sodium acetoacetate, 2-acetylbutyrolactone,ethyl ot-chloroacetoacetate and phenylhydrazone dehydroacetate.

35. The method of claim 1, wherein said methylene compound and saidvinyl compound are contained in the silver halide photographic emulsion.I

36. The method of claim 1, wherein only one of said methylene compoundor vinyl compound is contained in the silver halide photographicemulsion.

37. A method for forming a polymer image from a reaction systemconsisting essentially of a silver halide emulsion, an active methylcompound, and at least one addition-polymerizable vinyl monomer orvinylidene monomer which comprises developing a silver halidephotographic emulsion having a latent image with at least one activemethylene compound represented by the following General Formulas (a),(b) or (c), tautomeric isomers thereof and metal complex salts thereof,in the presence of at least one addition-polymerizable member selectedfrom the group consisting of vinyl monomers and vinylidene monomers topolymerize said monomer selectively at the latent image areas, saidsilver halide acting as an oxidizer, said polymerization being initiatedby the oxidizing intermediate product formed from the reactivity betweensaid active methylene compound and said silver halide:

General Formula (a) wherein R and R are members selected from the groupconsisting of an alkyl group, a substituted alkyl group, and asubstituted phenyl group, R is a member selected from the groupconsisting of a hydrogen atom, an alkyl group and a substituted alkylgroup, said R being capable of forming a ring with R or R GeneralFormula (b) wherein R is a member selected from the group consisting ofa hydrogen atom and an alkyl group, R is a member selected from thegroup consisting of an alkyl group, a substituted aromatic ring, andsodium, R is a member selected from the group consisting of a hydrogenatom, an alkyl group, a substituted alkyl group, a cyano group and achlorine atom, R and R capable of forming a ring, R being an aromaticring when X is -NH-- and a member selected from the group consisting ofan acyl group and an alkyl group when X is -O', X is a member selectedfrom the group consisting of O, NH, and

and Y is a member selected from the group consisting of O and NH; and

General Formula (0) wherein R is a member selected from the groupconsisting of a hydrogen atom, an acyl group and a phenyl group, and Ris a member selected from the group consisting of an ethoxy carbonylgroup and a cyano group, said alkyl and substituted alkyl groupcontaining less than 17 carbon atoms, said substituent for saidsubstituted alkyl group being selected from the group consisting ofcarbonyl, ester, halide, and carboxylic acid, said ring which R can formwith R or R being selected from the group consisting of a six-memberedring of saturated or unsaturated hydrocarbons and a five to six-memberedheterocyclic ring containing therein .an oxygen or nitrogen atom, saidsubstituted aromatic ring being substituted with a member selected fromthe group consisting of methoxy, halide, nitro, acyl, carboxyl, sulphoneand hydroxyl, and said methylene compound being present in an amount offrom to 5 mols.

(References on following page) 23 References Cited 3,488,269 1/1970Allen et a1. 204-15923 UNITED STATES PATENTS RONALD H. SMITH, PrimaryExaminer 3,019,104 1/1962 Oster 9629 3,038,800 6/1962 Luckey et a1.96-351 5 3,010,442 12/1962 Cohen et a1. 96-115 9628, 35.1, 115 P

